Substitution and

Elimination
Edited by: Dr. Nadeem Sadiq Sheikh

Department of Chemistry, College of Science

King Faisal University, Saudi Arabia
https://sites.google.com/site/243chem

Substitution, Nucleophilic,
Bimolecular SN2
Nuc :

Nuc

Nuc

transition state

Rate = k[Nuc: ][R-X]

Second Order Rate Kinetics

+ X

Stereochemistry of SN2
Reaction
Inversion of Configuration
CN

Br
+
(S)

KCN

+ KBr
(R)

Inversion on a Ring is often

more Obvious: Cis
Trans

Substrate Reactivity
Since the energy of the transition state is significant in determining
the rate of the reaction, a primary substrate will react more rapidly
than secondary (which is much more rapid than tertiary).
R
Rate: ~0

Br + Cl
1

Cl + Br

500

40,000

2 x 10

(CH3)3CBr

(CH3)3CCH2Br

(CH3)2CHBr

CH3CH2Br

CH3Br

tertiary

neopentyl

secondary

primary

methyl

1o > 2o >> 3o
Bulkiness of Substrate

Nucleophilicity
Nucleophile strength roughly parallels basicity
-

CH3 > NH2 > OH > F

Nucleophile strength increases going down a group

OH < SH
-

F < Cl < Br < I

NH3 < PH3

A base is always a stronger nucleophile than its conjugate acid
-

NH2 > NH3

-

OCH3 > CH3OH

Bimolecular Elimination E2
Nucleophile acts as Bronsted Base
Base:

H
C

C
Br

+ base-H
+ Br

-Elimination

Base

H
C

Br

SN2 Competes with E2

Depends on the Size of the Base
CH3CH2O
str. base
CH3CH2CH2CH2Br
(CH3)3CO

CH3CH2CH2CH2OEt
90%

CH3CH2CH=CH2
10%

CH3CH2CH2CH2OtBu CH3CH2CH=CH2
str. bulky base
85%
15%

SN2 Competes with E2

Depends on the Nature of the Substrate
CN
CH3CH2CH2CH2Br
CH3CH2CH2CH2CN
str. nuc.; wk. base
100% SN2
1o

(CH3)3CBr
3o

CN

CH2=C(CH3)2
100% E2

Stereochemistry of E2
rate = k[R-X][base]
second order rate kinetics
CH3O

H
C

C
Br

H on carbon is anti to leaving group

+ CH3OH
+ Br

SN2 and E2
SN2
H
R1 C
R2

Nuc:

C
Br

Nuc

R1 C
R2

+ Br

E2
H
R1 C
R2

B:
Br
rate = k[R-Br][B-]

R1
R2

+ B-H + Br

Unimolecular Substitution
and Elimination SN1 and
E1
CH3
CH3

Br

in warm CH3OH

CH3
Rate = k[R-Br]
1st order rate kinetics

CH3
CH3

C
CH3
SN1

CH3
OCH3 +

C=CH2
CH3

+ HBr
E1

E1 Mechanism

SN1 mechanism (Wade)

1st step is rate determining

Reaction Profiles (Wade)

SN 1
S N2

Carbocation Stability
more highly substituted, lower
energy

Carbocation Stability

CH3
CH3

H
> CH3

CH3
tertiary

>

= CH2=CH CH2 =

CH3
secondary = primary allylic

CH2 > CH3CH2

=

primary benzylic > primar

resonance stabilized